CN117393667A - LED epitaxial wafer, preparation method thereof and LED - Google Patents
LED epitaxial wafer, preparation method thereof and LED Download PDFInfo
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- 229910002704 AlGaN Inorganic materials 0.000 claims description 8
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
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Abstract
The invention discloses a light-emitting diode epitaxial wafer and a preparation method thereof, and an LED, wherein the light-emitting diode epitaxial wafer comprises a substrate, and a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer are sequentially arranged on the substrate; the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated. The LED epitaxial wafer provided by the invention can reduce the polarization effect of the multiple quantum well layers, improve the crystal quality of the quantum well layers and improve the luminous efficiency of the multiple quantum well layers.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a light-emitting diode epitaxial wafer, a preparation method thereof and an LED.
Background
Group iii nitride semiconductor materials, typically GaN, including AlN, gaN, inN and its corresponding ternary alloy InGaN, inAlN, alGaN and quaternary alloy AlInGaN, have received great attention for their application in the optoelectronic field and in microwave devices. The InGaN alloy based on GaN material has its forbidden bandwidth adjustable In the whole visible wavelength range by regulating the In component In the alloy. Light Emitting Diodes (LEDs) fabricated with InGaN/GaN quantum wells as light emitting multiple quantum well layers have been widely used in the field of lighting and communications.
Currently commercialized high-efficiency GaN-based blue-green light emitting diodes generally employ InGaN quantum well layers/AlGaN quantum barrier layers as active regions. Therefore, the high-quality InGaN quantum well layer/AlGaN quantum barrier layer is a key for realizing the high-efficiency and high-brightness luminous tube. But the InGaN quantum well layer/AlGaN quantum barrier layer has the following problems:
first, the higher In composition In InGaN quantum wells increases the lattice mismatch with the GaN barrier, resulting In a large piezoelectric field In InGaN quantum wells, producing the so-called Quantum Confined Stark Effect (QCSE). The QCSE effect reduces the degree of coupling between the electron and hole wave functions in the quantum well, thereby reducing the internal quantum efficiency of the LED. Second, the polarization electric field caused by the larger lattice mismatch in the quantum well can tilt the energy band of the LED, further exacerbating the reduction in light output of the green LED.
Disclosure of Invention
The invention aims to solve the technical problem of providing a light-emitting diode epitaxial wafer which reduces the polarization effect of a multi-quantum well layer, improves the crystal quality of the quantum well layer and improves the luminous efficiency of the multi-quantum well layer.
The invention also aims to provide a preparation method of the light-emitting diode epitaxial wafer, which has simple process and can stably prepare the light-emitting diode epitaxial wafer with good luminous efficiency.
In order to solve the technical problems, the invention provides a light-emitting diode epitaxial wafer, which comprises a substrate, wherein a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer are sequentially arranged on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated;
the C/Si co-doped GaN layer has a C doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 ；
The C/Si co-doped GaN layer has Si doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 。
In one embodiment, the thickness of the C/Si co-doped GaN layer is 0.5 nm-5 nm.
In one embodiment, the thickness of the nitrogen polar GaN layer is 0.5 nm-5 nm;
the nitrogen polar GaN layer is obtained by nitriding the GaN layer, wherein the nitriding treatment is that NH is adopted at 900-1100 DEG C 3 And (5) performing nitriding treatment.
In one embodiment, the thickness of the transition InGaN layer is 0.5 nm-5 nm;
the In component of the transition InGaN layer is 0.01-0.3;
the In composition of the transition InGaN layer gradually increases along the growth direction.
In one embodiment, the thickness of the InGaN layer is 0.5 nm-5 nm;
the In component of the InGaN layer is 0.01-0.3;
the In composition In the InGaN layer remains unchanged.
In one embodiment, the InGaN/GaN cap layer comprises an InGaN graded layer and an N-type GaN layer stacked in sequence;
the thickness of the InGaN/GaN cap layer is 0.5 nm-5 nm;
in one embodiment, the In component of the InGaN graded layer is 0.01-0.3;
the In composition of the InGaN graded layer gradually decreases along the growth direction.
In one embodiment, the multiple quantum well layer comprises a composite quantum well layer and a quantum barrier layer which are alternately laminated for 1-20 periods;
the quantum barrier layer is an AlGaN layer.
In order to solve the problems, the invention also provides a preparation method of the light-emitting diode epitaxial wafer, which comprises the following steps:
s1, preparing a substrate;
s2, sequentially depositing a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated;
the C/Si co-doped GaN layer has a C doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 ；
The C/Si co-doped GaN layer has Si doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 。
Correspondingly, the invention further provides an LED, and the LED comprises the LED epitaxial wafer.
The implementation of the invention has the following beneficial effects:
the light-emitting diode epitaxial wafer provided by the invention is provided with a multiple quantum well layer with a specific structure, wherein the multiple quantum well layer comprises a plurality of alternately laminated composite quantum well layers and quantum barrier layers, and the composite quantum well layers comprise a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are laminated in sequence.
The GaN-based LED grown on the sapphire substrate has an external delay, and an internal electrostatic field exists in the multiple quantum well layer due to spontaneous polarization and piezoelectric polarization effects. The C/Si co-doped GaN layer can reduce the internal electrostatic field effect of the multi-quantum well layer, reduce the quantum confinement Stark effect, improve the coupling degree between quantum well electrons and hole wave functions, and improve the luminous efficiency of the quantum well. Depositing an InGaN layer on the nitrogen-polar GaN layer can reduce polarization effects and reduce LED band bending. The In component of the transitional InGaN layer gradually rises, so that lattice mismatch between the C/Si co-doped GaN layer and the InGaN layer can be reduced, and piezoelectric polarization effect In the quantum well is eliminated. The InGaN layer can enable energy levels of electrons and holes to be discrete quantized energy levels, has obvious quantum confinement effect, and enables the electrons and the holes to be localized in the multiple quantum wells, so that overlapping of wave functions of the electrons and the holes is improved, and further radiation recombination rate is improved. The InGaN/GaN cap layer can reduce lattice mismatch between the InGaN layer and the GaN layer, and can also effectively protect the decomposition of the quantum well InGaN layer caused by overhigh deposition temperature of the P-type GaN layer, so that the damage to crystal quality is avoided.
In summary, by growing the multi-period composite quantum well layer and the quantum barrier layer, the quantum confinement effect can be improved, and electrons and holes are localized in the multi-quantum well, so that the overlap of the electron and hole wave functions is improved, the polarization effect of the multi-quantum well layer is reduced, the crystal quality of the quantum well layer is improved, and the luminous efficiency of the multi-quantum well layer is improved.
Drawings
Fig. 1 is a schematic structural diagram of an led epitaxial wafer according to the present invention;
fig. 2 is a flowchart of a method for preparing an led epitaxial wafer according to the present invention;
fig. 3 is a flowchart of step S2 of the method for manufacturing a light emitting diode epitaxial wafer according to the present invention.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent.
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in the present invention, "preferred" is merely to describe embodiments or examples that are more effective, and it should be understood that they are not intended to limit the scope of the present invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical range is referred to, and both ends of the numerical range are included unless otherwise specified.
In order to solve the above problems, the present invention provides a light emitting diode epitaxial wafer, as shown in fig. 1, comprising a substrate 100, wherein a buffer layer 200, an undoped GaN layer 300, an N-type GaN layer 400, a multiple quantum well layer 500, an electron blocking layer 600, and a P-type GaN layer 700 are sequentially disposed on the substrate 100;
the multiple quantum well layer 500 includes a plurality of composite quantum well layers 510 and quantum barrier layers 520 alternately stacked, and the composite quantum well layers 510 include C/Si co-doped GaN layers 511, nitrogen polarity GaN layers 512, transition InGaN layers 513, inGaN layers 514, and InGaN/GaN cap layers 515 stacked in sequence;
the C/Si co-doped GaN layer has a C doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 ；
The C/Si co-doped GaN layer has Si doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 。
The specific structure of the multiple quantum well layer 500 is as follows:
in one embodiment, the thickness of the C/Si co-doped GaN layer 511 is 0.5nm to 5nm; exemplary thicknesses of the C/Si co-doped GaN layer 511 are 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, but are not limited thereto. Preferably, the C/Si co-doped GaN layer 511 has a C doping concentration of 2×10 17 atoms/cm 3 ~9×10 17 atoms/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The C/Si co-doped GaN layer 511 has a Si doping concentration of 2×10 17 atoms/cm 3 ~9×10 17 atoms/cm 3 。
The GaN-based LED grown on the sapphire substrate has an external delay, and an internal electrostatic field exists in the multiple quantum well layer due to spontaneous polarization and piezoelectric polarization effects. The C/Si co-doped GaN layer 511 can reduce the internal electrostatic field effect of the multiple quantum well layer, reduce the quantum confinement stark effect, improve the coupling degree between the quantum well electron and hole wave functions, and improve the quantum well light-emitting efficiency.
In one embodiment, the thickness of the nitrogen polar GaN layer 512 is 0.5nm to 5nm, and the exemplary thickness of the nitrogen polar GaN layer 512 is 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, but not limited thereto. In one embodiment, the nitrogen polar GaN layer 512 is formed by nitriding a GaN layer with NH at 900-1100 DEG C 3 And (5) performing nitriding treatment. Depositing an InGaN layer on the nitrogen-polar GaN layer 512 may reduce polarization effects and reduce LED band bending.
In one embodiment, the thickness of the transition InGaN layer 513 is 0.5nm to 5nm; exemplary thicknesses of the transition InGaN layer 513 are 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, but are not limited thereto. In one embodiment, the In composition of the transition InGaN layer 513 is 0.01-0.3; preferably, the In composition of the transition InGaN layer 513 is 0.1-0.2; more preferably, the In composition of the transition InGaN layer 513 is gradually increased In the growth direction. The In composition of the transition InGaN layer 513 gradually increases, so that lattice mismatch between the C/Si co-doped GaN layer 511 and the InGaN layer 514 can be reduced, and piezoelectric polarization effect In the quantum well is eliminated.
In one embodiment, the thickness of the InGaN layer 514 is 0.5nm to 5nm; exemplary thicknesses of the InGaN layer 514 are 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, but are not limited thereto. In one embodiment, the In composition of the InGaN layer 514 is 0.01-0.3; preferably, the In composition of the InGaN layer 514 is 0.1-0.2; more preferably, the In composition within the InGaN layer 514 remains unchanged. The InGaN layer 514 can make the energy levels of electrons and holes become discrete quantized energy levels, and has a remarkable quantum confinement effect, and the electrons and the holes are localized in the multiple quantum wells, so that the overlap of the wave functions of the electrons and the holes is improved, and the radiation recombination rate is further improved.
In one embodiment, the InGaN/GaN cap layer 515 includes an InGaN graded layer and an N-type GaN layer stacked in sequence; the thickness of the InGaN/GaN cap layer 515 is 0.5 nm-5 nm; exemplary thicknesses of the InGaN/GaN cap layer 515 are 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, but are not limited thereto. In one embodiment, the In component of the InGaN graded layer is 0.01-0.3; preferably, the In component of the InGaN graded layer is 0.1-0.2; more preferably, the In composition of the InGaN graded layer gradually decreases In the growth direction. The InGaN/GaN cap layer 515 can reduce lattice mismatch between the InGaN layer and the GaN layer, and can also effectively protect the quantum well InGaN layer from decomposition due to the too high deposition temperature of the P-type GaN layer, so as to avoid damaging the crystal quality.
In one embodiment, the multiple quantum well layer comprises a composite quantum well layer and a quantum barrier layer which are alternately laminated for 1-20 periods; exemplary cycle numbers are 2, 4, 6, 8, 10, 12, 14, 16, 18, but are not limited thereto. In one embodiment, the quantum barrier layer is an AlGaN layer. The proper quantum barrier layer can not only reduce non-radiative recombination caused by overflow of electrons to the P-type layer, but also improve the recombination efficiency of electrons and holes in the quantum well.
In summary, by growing the multi-period composite quantum well layer and the quantum barrier layer, the quantum confinement effect can be improved, and electrons and holes are localized in the multi-quantum well, so that the overlap of the electron and hole wave functions is improved, the polarization effect of the multi-quantum well layer is reduced, the crystal quality of the quantum well layer is improved, and the luminous efficiency of the multi-quantum well layer is improved.
Correspondingly, the invention provides a preparation method of the light-emitting diode epitaxial wafer, as shown in fig. 2, comprising the following steps:
s1, preparing a substrate 100;
the substrate can be sapphire substrate or SiO 2 One of a sapphire composite substrate, a silicon carbide substrate, a gallium nitride substrate and a zinc oxide substrate.
Preferably, the substrate is a sapphire substrate, which is the most commonly used GaN-based LED substrate material at present, and the sapphire substrate has the advantages of mature preparation process, low price, easy cleaning and processing and good stability at high temperature.
S2, a buffer layer 200, an undoped GaN layer 300, an N-type GaN layer 400, a multiple quantum well layer 500, an electron blocking layer 600 and a P-type GaN layer 700 are sequentially deposited on the substrate 100.
As shown in fig. 3, the step S2 specifically includes the following steps:
s21, depositing a buffer layer 200 on the substrate 100.
In one embodiment, an AlN buffer layer is deposited in PVD, with a thickness of 10 nm-20 nm. The AlN buffer layer provides a nucleation center which is the same as the substrate orientation, stress generated by lattice mismatch between GaN and the substrate and thermal stress generated by thermal expansion coefficient mismatch are released, further growth provides a flat nucleation surface, and the contact angle of nucleation growth is reduced to enable island-shaped GaN grains to be connected into a plane in a smaller thickness, so that the island-shaped GaN grains are converted into two-dimensional epitaxial growth.
Preferably, the sapphire substrate on which the AlN buffer layer has been plated is transferred into MOCVD at H 2 The atmosphere is preprocessed for 1 min-10 min, the processing temperature is 1000 ℃ to 1200 ℃, and then the sapphire substrate is nitrided, so that the crystal quality of the AlN buffer layer is improved, and the crystal quality of a subsequent deposited GaN epitaxial layer can be effectively improved.
S22, depositing an undoped GaN layer 300 on the buffer layer 200.
In one embodiment, the temperature of the reaction chamber is controlled to 1050-1200 ℃, the pressure is controlled to 100-600 torr, an N source and a Ga source are introduced, and an undoped GaN layer with the thickness of 1-5 μm is grown.
S23, depositing an N-type GaN layer 400 on the undoped GaN layer 300.
In one embodiment, the temperature of the reaction chamber is controlled at 1050-1200 ℃, the pressure is controlled at 100-600 torr, and the N-type GaN layer is grown by introducing an N source, a Ga source and a Si source.
S24, depositing a multiple quantum well layer 500 on the N-type GaN layer 400.
The multiple quantum well layer 500 includes a plurality of composite quantum well layers 510 and quantum barrier layers 520 alternately stacked, and the composite quantum well layers 510 include a C/Si co-doped GaN layer 511, a nitrogen polarity GaN layer 512, a transition InGaN layer 513, an InGaN layer 514, and an InGaN/GaN cap layer 515, which are sequentially stacked.
In one embodiment, the C/Si co-doped GaN layer 511 is fabricated by the following method:
the temperature of the reaction chamber is controlled to be 820-900 ℃, the pressure is controlled to be 50-500 torr, and N 2 And NH 3 Mixed atmosphere, N 2 And NH 3 The ratio of the mixture to the GaN layer is 1:1-1:10, and the N source, the C source, the Ga source and the Si source are introduced to grow the C/Si co-doped GaN layer.
In one embodiment, the nitrogen polar GaN layer 512 is fabricated by the following method:
the temperature of the reaction chamber is controlled to be 800-850 ℃, the pressure is controlled to be 50-500 torr, and N 2 And NH 3 Mixed atmosphere, N 2 And NH 3 The ratio of the N source to the Ga source is 1:1-1:10, and a GaN layer is grown;
the GaN adopts NH at 900-1100 DEG C 3 And performing nitriding treatment to obtain the nitrogen polar GaN layer.
In one embodiment, the transition InGaN layer 513 is fabricated by the following method:
the temperature of the reaction chamber is controlled to be 750-820 ℃, the pressure is controlled to be 50-500 torr, and N 2 And NH 3 Mixed atmosphere, N 2 And NH 3 The ratio of the lead-In is 1:1-1:10, and the N source, the In source and the Ga source are led In to grow the transitional InGaN layer.
Preferably, the In component of the transitional InGaN layer is gradually increased by regulating and controlling the temperature change, so that lattice mismatch In the quantum well layer is reduced, and piezoelectric polarization effect In the quantum well is eliminated.
In one embodiment, the InGaN layer 514 is made by the following method:
the temperature of the reaction chamber is controlled to be 750-820 ℃, the pressure is controlled to be 50-500 torr, and N 2 And NH 3 Mixed atmosphere, N 2 And NH 3 The ratio of the InGaN layer to the N source, the In source and the Ga source is 1:1-1:10, and the InGaN layer is grown.
In one embodiment, the InGaN/GaN cap layer 515 is made by the following method:
the temperature of the reaction chamber is controlled to be 750-900 ℃, the pressure is controlled to be 50-500 torr, and N 2 And NH 3 Mixed atmosphere, N 2 And NH 3 The ratio of the InGaN graded layer to the N source, the In source and the Ga source is 1:1-1:10;
the temperature of the reaction chamber is controlled to be 750-900 ℃, the pressure is controlled to be 50-500 torr, and N 2 And NH 3 Mixed atmosphere, N 2 And NH 3 The ratio of the N source to the N-type doping agent to the Ga source is 1:1-1:10, and the N-type GaN layer is grown.
Preferably, in the growth process of the InGaN graded layer, the flow of the In source and the Ga source is kept unchanged, the temperature is gradually increased, and the In component is reduced along with the temperature increase, so as to obtain the InGaN graded layer.
In one embodiment, the quantum barrier layer 520 is fabricated using the following method:
and controlling the temperature of the reaction chamber at 800-1000 ℃ and the pressure at 50-500 torr, and introducing an N source, an Al source and a Ga source to grow the AlGaN quantum barrier layer.
S25, depositing an electron blocking layer 600 on the multiple quantum well layer 500.
In one embodiment, the temperature of the reaction chamber is controlled to be 900-1000 ℃, the pressure is controlled to be 100-300 torr, an N source, an Al source, a Ga source and an In source are introduced, and an AlInGaN electron blocking layer with the thickness of 10-40 nm is grown.
S26, a P-type GaN layer 700 is deposited on the electron blocking layer 600.
In one embodiment, the temperature of the reaction chamber is controlled to 900-1050 ℃, the pressure is controlled to 100-600 torr, an N source, a Ga source and an Mg source are introduced, and a P-type GaN layer with the thickness of 10-5 nm is grown. Preferably, the Mg doping concentration is 1×10 19 atoms/cm 3 ~1×10 21 atoms/cm 3 。
Correspondingly, the invention further provides an LED, and the LED comprises the LED epitaxial wafer. The photoelectric efficiency of the LED is effectively improved, and other items have good electrical properties.
The invention is further illustrated by the following examples:
example 1
The embodiment provides a light-emitting diode epitaxial wafer, which comprises a substrate, wherein a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer are sequentially arranged on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated.
The thickness of the C/Si co-doped GaN layer is 2nm, and the C doping concentration is 5 multiplied by 10 17 atoms/cm 3 Si doping concentration of 6.5X10 17 atoms/cm 3 。
The thickness of the nitrogen polar GaN layer is 1.5nm.
The thickness of the transitional InGaN layer is 1nm, and the in component gradually increases from 0.05 to 0.15 along the growth direction.
The thickness of the InGaN layer was 3.5nm, and the in composition was 0.15.
The thickness of the InGaN/GaN cap layer is 2.5nm, the InGaN/GaN cap layer comprises an InGaN graded layer and an N-type GaN layer which are sequentially stacked, and the In component of the InGaN graded layer is gradually reduced from 0.15 to 0.05 along the growth direction.
Example 2
The embodiment provides a light-emitting diode epitaxial wafer, which comprises a substrate, wherein a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer are sequentially arranged on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated.
The thickness of the C/Si co-doped GaN layer is 1nm, and the C doping concentration is 1 multiplied by 10 17 atoms/cm 3 Si doping concentration of 1×10 17 atoms/cm 3 。
The thickness of the nitrogen polar GaN layer is 1nm.
The thickness of the transitional InGaN layer is 1nm, and the in component gradually increases from 0.01 to 0.3 along the growth direction.
The thickness of the InGaN layer was 1nm, and the in composition was 0.15.
The thickness of the InGaN/GaN cap layer is 1nm, the InGaN/GaN cap layer comprises an InGaN graded layer and an N-type GaN layer which are sequentially stacked, and the In component of the InGaN graded layer is gradually reduced from 0.3 to 0.1 along the growth direction.
Example 3
The embodiment provides a light-emitting diode epitaxial wafer, which comprises a substrate, wherein a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer are sequentially arranged on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated.
The thickness of the C/Si co-doped GaN layer is 5nm, and the C doping concentration is 1 multiplied by 10 18 atoms/cm 3 Si doping concentration of 1×10 18 atoms/cm 3 。
The thickness of the nitrogen polar GaN layer is 5nm.
The thickness of the transitional InGaN layer is 5nm, and the in component gradually increases from 0.1 to 0.2 along the growth direction.
The thickness of the InGaN layer was 5nm, and the in composition was 0.15.
The thickness of the InGaN/GaN cap layer is 5nm, the InGaN/GaN cap layer comprises an InGaN graded layer and an N-type GaN layer which are sequentially stacked, and the In component of the InGaN graded layer is gradually reduced from 0.2 to 0.1 along the growth direction.
Comparative example 1
This comparative example provides a light emitting diode epitaxial wafer, which is different from embodiment 1 in that: the multiple quantum well layer is an InGaN quantum well layer/AlGaN quantum barrier layer, and the rest is referred to in example 1.
Comparative example 2
This comparative example provides a light emitting diode epitaxial wafer, which is different from embodiment 1 in that: the composite quantum well layer comprises a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially stacked, and does not comprise a C/Si co-doped GaN layer, and the rest refers to the embodiment 1.
Comparative example 3
This comparative example provides a light emitting diode epitaxial wafer, which is different from embodiment 1 in that: the composite quantum well layer comprises a C/Si co-doped GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated, and does not comprise a nitrogen polar GaN layer, and the rest refers to the embodiment 1.
Comparative example 4
This comparative example provides a light emitting diode epitaxial wafer, which is different from embodiment 1 in that: the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated, and does not comprise a transition InGaN layer, and the rest refers to the embodiment 1.
Comparative example 5
This comparative example provides a light emitting diode epitaxial wafer, which is different from embodiment 1 in that: the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer and an InGaN layer which are sequentially laminated, and does not comprise an InGaN/GaN cap layer, and the rest refers to the embodiment 1.
The light emitting diode epitaxial wafers prepared in examples 1 to 3 and comparative examples 1 to 5 were prepared into 10mil×24mil chips using the same chip process conditions, 300 LED chips were extracted, and tested at 120mA/60mA current, and the luminous efficiency improvement rates of each example and comparative example were calculated with reference to comparative example 1, and the specific test results are shown in table 1.
Table 1 results of Performance test of LEDs prepared in examples 1 to 3 and comparative examples 1 to 5
From the above results, it can be seen that the present invention can improve quantum confinement effect by growing the composite quantum well layer and the quantum barrier layer in multiple cycles by providing the composite quantum well layer having a specific structure on the substrate, and the electrons and holes are localized in the multiple quantum wells, thereby improving overlap of the electron and hole wave functions, reducing polarization effect of the multiple quantum well layer, improving crystal quality of the quantum well layer, and improving luminous efficiency of the multiple quantum well layer.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (10)
1. The light-emitting diode epitaxial wafer is characterized by comprising a substrate, wherein a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer are sequentially arranged on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated;
the C/Si co-doped GaN layer has a C doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 ；
The C/Si co-doped GaN layer has Si doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 。
2. The light-emitting diode epitaxial wafer of claim 1, wherein the C/Si co-doped GaN layer has a thickness of 0.5nm to 5nm.
3. The light-emitting diode epitaxial wafer of claim 1, wherein the nitrogen polar GaN layer has a thickness of 0.5nm to 5nm;
the nitrogen polar GaN layer is obtained by nitriding the GaN layer, wherein the nitriding treatment is that NH is adopted at 900-1100 DEG C 3 And (5) performing nitriding treatment.
4. The light-emitting diode epitaxial wafer of claim 1, wherein the thickness of the transition InGaN layer is 0.5 nm-5 nm;
the In component of the transition InGaN layer is 0.01-0.3;
the In composition of the transition InGaN layer gradually increases along the growth direction.
5. The light-emitting diode epitaxial wafer of claim 1, wherein the InGaN layer has a thickness of 0.5nm to 5nm;
the In component of the InGaN layer is 0.01-0.3;
the In composition In the InGaN layer remains unchanged.
6. The light emitting diode epitaxial wafer of claim 1, wherein the InGaN/GaN cap layer comprises an InGaN graded layer and an N-type GaN layer stacked in sequence;
the thickness of the InGaN/GaN cap layer is 0.5 nm-5 nm.
7. The light-emitting diode epitaxial wafer of claim 6, wherein the In composition of the InGaN graded layer is 0.01-0.3;
the In composition of the InGaN graded layer gradually decreases along the growth direction.
8. The light-emitting diode epitaxial wafer of claim 1, wherein the multiple quantum well layer comprises a composite quantum well layer and a quantum barrier layer alternately stacked for 1 to 20 cycles;
the quantum barrier layer is an AlGaN layer.
9. A method for preparing the light-emitting diode epitaxial wafer according to any one of claims 1 to 8, comprising the following steps:
s1, preparing a substrate;
s2, sequentially depositing a buffer layer, an undoped GaN layer, an N-type GaN layer, a multiple quantum well layer, an electron blocking layer and a P-type GaN layer on the substrate;
the multi-quantum well layer comprises a plurality of composite quantum well layers and quantum barrier layers which are alternately laminated, wherein the composite quantum well layer comprises a C/Si co-doped GaN layer, a nitrogen polar GaN layer, a transitional InGaN layer, an InGaN layer and an InGaN/GaN cap layer which are sequentially laminated;
the C/Si co-doped GaN layer has a C doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 ；
The C/Si co-doped GaN layer has Si doping concentration of 1×10 17 atoms/cm 3 ~1×10 18 atoms/cm 3 。
10. An LED, characterized in that the LED comprises a light emitting diode epitaxial wafer according to any one of claims 1 to 8.
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